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Inorg. Chem. 1996, 35, 7394-7398
K(VO)(SeO3)2H: A New One-Dimensional Compound with Strong Hydrogen Bonding Yoon Hyun Kim, Kyu-Seok Lee, and Young-Uk Kwon* Department of Chemistry, Sung Kyun Kwan University, Suwon, 440-746, Korea
Oc Hee Han Korea Basic Science Institute, Taejeon, 305-333, Korea ReceiVed May 28, 1996X
The hydrothermal synthesis, X-ray single crystal structure, magnetic properties, and solid state NMR and infrared spectroscopic data of a new compound, K(VO)(SeO3)2H, are described. K(VO)(SeO3)2H crystallizes in the monoclinic space group P21/m (No. 11), with a ) 7.8659(7) Å, b ) 10.4298(7) Å, c ) 4.0872(7) Å, β ) 96.45(1)°, and Z ) 4. The structure is described as parallel linear strands made of repeating [(VO)(SeO3)2]2- units. The chains are held together through hydrogen bondings between selenite oxygens, weak VdO‚‚‚VdO bonds, and ionic bonds to the interchain K+ ions. The hydrogen bonding in this compound shows many characteristics of the strong hydrogen bonding with a short O-O distance of 2.459(6) Å, a large down field shift of the proton NMR signal of 19 ( 1 ppm, and a low O-H absorption frequency. However, the exact position of the hydrogen atom and, thus, the nature of the hydrogen bonding in this compound is unclear. Possible models for the hydrogen atom positions are discussed based on experimental and literature data. The magnetic susceptibility data show an antiferromagnetic coupling below 19 K. The curve can be explained with a 1-D Heisenberg model for S ) 1/ with J/k ) 13.8 K and g ) 1.97. 2
Introduction Vanadium(IV) oxo compounds, especially those synthesized by hydrothermal reactions, are attracting much interest because of the variety of structures and the magnetic properties.1,2 This class of materials have been found mainly from vanadiumphosphate and -phosphonate systems,2 and some from the vanadium-selenite systems.3-6 Interest in the selenite compounds stems from the expected structural similarity between SeO32- ion and PO43-/RPO32- ions. Examples of vanadium(IV) selenites in the literature are VOSeO3‚H2O,3 AV2SeO7 (A ) K and Rb),4,5 and Ba(VO)2(SeO3)2(HSeO3)26 which show dimer, one-dimensional antiferromagnetic, and no magnetic couplings, respectively. There are also VOSeO3 and VOSe2O5 reported in the literature.7,8 X Abstract published in AdVance ACS Abstracts, November 1, 1996. (1) (a) Riou, D.; Ferey, G. Inorg. Chem. 1995, 34, 6520. (b) Oka, Y.; Yao, T.; Yamamoto, N. J. Solid State Chem. 1995, 117, 407. (c) Oka, Y.; Tamada, O.; Yao, T.; Yamamoto, N. J. Solid State Chem. 1995, 114, 359. (2) (a) Bonavia, G.; Debord, J.; Haushalter, R. C.; Rose, D.; Zubieta, J. Chem. Mater. 1995, 7, 1995 and references therein. (b) Mueller, A.; Hovemeier, K.; Krickemeyer, E.; Boegge, H. Angew. Chem., Int. Ed. Engl. 1995, 34, 779. (c) Harrison, W. T. A.; Hsu, K.; Jacobson, A. J. Chem. Mater. 1995, 7, 2004. (d) Harrison, W. T. A.; Lim, S. C.; Vaughey, J. T.; Jacobson, A. J.; Goshorn, D. P.; Johnson, J. W. J. Solid State Chem. 1994, 113, 444. (e) Lii, K. H.; Wen, N. S.; Su, C. C.; Chen, B. R. Inorg. Chem. 1992, 31, 439 and references therein. (f) Haushalter, R. C.; Wang, Z.; Thomson, M. E.; Zubieta, J. Inorg. Chem. 1993, 32, 3700 and references therein. (3) Huan, G.; Johnson, J. W.; Jacobson, A. J.; Goshorn, D. P. Chem. Mater 1991, 3, 539. (4) Lee, K.-S.; Kwon, Y.-U.; Namgung, H.; Kim, S.-H. Inorg. Chem. 1995, 34, 4178. (5) Kim, Y.-H.; Kwon, Y.-U. Bull. Korean Chem. Soc., in press. (6) Harrison, W. T. A.; Vaughey, J. T.; Jacobson, A. J.; Goshorn, D. P.; Johnson, J. W. J. Solid State Chem. 1995, 116, 77. (7) Trombe, J. C.; Enjalbert, R.; Gleizes, A.; Galy, J. C. R. Acad. Sci., Ser. 2 1983, 297, 667. (8) Trombe, J. C.; Gleizes, A.; Galy, J.; Renard, J. P.; Journaux, Y.; Verdaguer, M. New J. Chem. 1987, 11, 331.
S0020-1669(96)00624-6 CCC: $12.00
During our investigation on the hydrothermal reactions of various vanadium selenite systems,4,5,9 we have obtained a new compound K(VO)(SeO3)2H with an 1D-chain structure. This compound exhibits a so-called strong hydrogen bonding with a short O‚‚‚O distance of 2.459(6) Å.10-13 The strong hydrogen bonding has been the subject of many papers in enzyme kinetics,14-16 physical organic,12,13,17,18 and solid state crystal chemistry.11 Such hydrogen bondings are found when the donor and acceptor atoms are closer than the sum of their van der Waals radii (
